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Sphere-to-cylinder transition in hierarchical electrostatic complexes

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Abstract

We report on the formation of colloidal complexes resulting from the electrostatic co-assembly between anionic surfactants and cationic polyelectrolytes or block copolymers. Combining light and X-ray scattering experiments with cryogenic transmission and optical microscopy, we emphasize a feature rarely addressed in the formation of the electrostatic complexes, namely the role of the mixing concentration on the microstructure. At low mixing concentration, electrostatic complexes made from cationic-neutral copolymers and alkyl sulfate surfactants exhibit spherical core-shell microstructures. With increasing concentration, the complexes undergo a sphere-to-cylinder transition, yielding elongated aggregates with diameter 50 nm and length up to several hundreds of nanometers. From the comparison between homo- and diblock polymer phase behaviors, it is suggested that the unidimensional growth is driven by the ability of the surfactant to self-assemble into cylindrical micelles when complexed with cationic polymers.

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Acknowledgments

I am grateful to Ling Qi, Jean-Paul Chapel, Pascal Hervé, and Jean-Christophe Castaing from the Complex Fluids Laboratory (CRTB Rhodia, Bristol, Pa) for discussions and comments during the course of this study. I am also indebted to Annie Vacher and Marc Airiau (Centre de Recherches d’Aubervilliers, Rhodia, France) for the cryo-TEM experiments on the mixed systems. This SAXS runs were carried out at the National Synchrotron Light Source, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Division of Materials Sciences and Division of Chemical Sciences, under contract no. DE-AC02-98CH10886. This research is supported in part by Rhodia.

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  1. Matière et Systèmes Complexes, UMR 7057 CNRS Université Denis Diderot Paris-VII, Bâtiment Condorcet, 10 rue Alice Domon et Léonie Duquet, 75205, Paris, France

    J.-F. Berret

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Correspondence to J.-F. Berret.

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Berret, JF. Sphere-to-cylinder transition in hierarchical electrostatic complexes. Colloid Polym Sci 287, 801–810 (2009). https://doi.org/10.1007/s00396-009-2032-1

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